Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

• This invention relates to the preparation of acrylonitrile fibers. More particularly, it relates to new compositions of matter containing acrylonitrile polymers which are capable of being spun into fibers having a high degree of luster stability.
• acrylonitrile fibers which have an initial uniform luster have been produced.
• such fibers generally tend to lose their luster during normal textile processing operations.
• the initially lustrous fibers usually become somewhat delustered on exposure to the hot-wet conditions utilized in washing, steam pressing, bleaching, and dyeing of the fabrics, yarns, rovings, staple, or other fiber forms.
• This loss of luster is generally observed as a dulling in an undyed material, or dulling and lightening of dye shades in I dyed materials. It is especially objectionable where nonuniformities occur in a single textile article as a result of localized variations in the treating conditions.
• an object of this invention to provide fibers of polymers of acrylonitrile which have a high initial luster.
• Another object of this invention is to provide lustrous acrylonitrile fibers which retain a high degree of luster during normal textile processing and use.
• a further object of this invention is to provide a homogeneous solution capable of being spun into fiberswhich have a lasting luster.
• R and R represent haloalkoxy radicals having 1 to 5 carbon atoms in the alkyl chain and from 1 to 4 substituted halogen atoms on the chain, and R is selected from the group consistingof hydroxyl and haloalkoxy radicals of the type just described, the combined total of said halogen atoms in the haloalkyl phosphate being at least 3.
• the spinning solution described is then extruded through orifices of a spinneret to form fibers according to known procedures.
• improved spinning properties are obtained by adding the haloalkyl phosphate to the spinning solution.
• a lower amount of solvent may be included in the solution as compared to that obtainable when the solution does not include the phosphate ester. This facilitates the spinning of heavy denier filaments.
• an acrylonitrile polymer may be prepared in a conventional manner such as that described in U.S. 2,628,223, U.S. 2,748,106, or U.S. 2,777,832.
• a homogeneous solution containing from about 5% to about 35% byweight of the polymer in an inert solvent is then prepared.
• Any of the known organic and inorganic solvents which are inert to the polymer may be used. Selection of the particular solvent Will generally depend on Whether a Wetor dry-spin ning technique is being used.
• organic solvents such as dimethylformamide dimethylacetamide, dimethyl rnethoxy-acetamide, N-formyl morpholine, N-formyl hexamethyleneimine, butadiene cyclic sulfone, tetramethylene cyclic sulfone, p-phenylene diamine, mand p-nitrophenols, and the like, may be used.
• inorganic solvents such as metal halides and thiocyanates, and those salts and mixed salts described in U.S. Patents 2,648,646 through 2,648,649 may be used.
• the phosphate ester is then added to the solution.
• the phosphate ester may be added simultaneously with or prior to the addition of the solvent, or to the freshly spun, solvent-laden filaments either prior to or.
• a stabilizer for the phosphate ester for example a compound which will react with hydrogen halide, such as a base, an active ethylenic compound, an epoxy compound and the like,
• a number of known methods may be used.
• a number of strands are Wrapped onto a rectangular frame.
• the frame is then immersed in a'material having a refractive index similar to that of the fibers to eliminate surface effects.
• the light transmitted through the fibers on the frame is then measured.
• Anisole has been found to be a suitable liquid for use with acrylonitrile polymer fibers.
• the degree of luster of various fiber samples can be conveniently computed by using the filter With peak transmission at 4200 A. Fibers having a luster of above are not considered appreciably delustered, while values of 60 and below represent appreciable delustering.
• the degree of delustering can be determined in dyed goods by observing the effectiveness of a given amount of dye in furnishing coloration. Deeper and brighter shades are obtained from fibers which are not delustered. Changes in fiber density are also indicative of changes in luster. In general, a high luster is associated with a high density.
• EXAMPLE I Ten parts of a polymer of 93.6% acrylonitrile, 6% methyl acrylate, and 0.4% sodium styrene-sulfonate, prepared by emulsion polymerization with a persulfate/ bisulfite redox catalyst system, were mixed under nitrogen with 20 parts dimethylformamide at a temperature of 50 C. with continuous stirring until a homogeneous solution was obtained. A haloalkyl phosphate was subsequently mixed into the homogeneous polymer solution; the nature and amount of haloalkyl phosphate being indicated by the data for separate experimental runs listed in the following table. The mixture was then spun at a temperature of 100 C. through a spinneret having 0.15 mm.
• haloalkyl phosphate As previously indicated, from about 5% to about 15% haloalkyl phosphate, based on the Weight of polymer, provides optimum results.
• the haloalkyl phosphates are generally completely miscible with the polymer at these levels of addition and yield clear, homogeneous fibers having unimpaired physical properties.
• haloalkyl phosphates which are slightly soluble, i.e., have a solubility up to about 0.5% in Water, confer permanent luster stability to the fibers when used according to the process of this invention.
• alkoxy groups may be selected from chloro-, iluoro-, and bromo-substituted methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tertiary butyl, and may be the same or different.
• Typical examples include tris-chloroethyl phosphate, tris-bromoethyl phosphate, chloro ethyl monopropyl phosphate, and 2,3-bromopropyl phosphoric acid.
• the bromoalkyl phosphates are generally preferred to the corresponding fluorine or chlorine compounds since they appear to provide better luster stabiliz ing properties and exhibit greater compatibility with polyacrylonitrile.
• spinning solutions containing acrylonitrile polymers in which the acrylonitrile component comprises at least of the polymer molecule may be prepared by the process of this invention.
• These polymers may contain one or more ethyleuically unsaturated monomers which are copolymerizablc with acrylonitrile. Examples of typical copolymerizable monomers are well known and may be found in US. Patents 2,436,926, 2,485,241, and 2,837,501.
• the polymers should preferably have an average molecular weight in the range of 40,000 to 150,000, and generally the molecular weight should be above 15,000 and should not exceed the value of 250,000.
• One of the primary advantages of the present invention resides in providing spinning solutions which may be extruded under pressure through a spinneret orifice to yield acrylonitrile fibers which have an initial uniform luster which remains substantially unchanged during subsequent processing.
• Another advantage residcs in the fact that the fibers prepared from the spinning solutions of this invention have high physical properties typical of fibers prepared from acrylonitrile polymers.
• spinability of the polymer solutions is improved, thus permitting a lower percentage of solvent in the solution as compared to spinning solutions heretofore known.
• a homogeneous spinning solution comprising an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% acrylonitrile and up to 30% by Weight of an ethylenically unsaturated monomer copolymerized therewith, an inert solvent for said polymer, and from about 3% to about 20% based on the weight of said polymer of a haloalkyl phosphate having the general formula wherein R R and R are haloalkoxy radicals having alkyl radicals selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl, and from 1 to 4 substituted halogen atoms selected from the group consisting of bromine and chlorine.
• composition of claim 1 in which the haloalkyl phosphate is tris(2,3-dibromopropyl)phosphate.
• composition of claim 1 wherein said solution contains from about 5% to about 35% by weight of said polymer.
• composition of claim 1 in which said polymer contains at least 85% acrylonitrile by weight in polymerized form and said solvent is N,N-dimethylforrnamide.
• a process for preparing filaments having a high degree of luster stability which comprises extruding a solution of an acrylonitrile polymer selected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% acrylonitrile, and up to by Weight of an ethylenically unsaturated monomer copolymerized therewith, containing from about 5 to about by weight of said polymer to form said filaments, treating said filaments in an aqueous bath containing from about 5% to about 20% of a haloalkyl phosphate having the general formula wherein R R and R are haloalkoxy radicals having alkyl radicals selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl and from 1 to 4 substituted halogen atoms selected from the group consisting of bromine and chlorine, for a period suflicient to permit said filaments to absorb
• a process for preparing filaments having a high degree of luster stability which comprises extruding a homogeneous solution comprising from about 5% to about 35% by weight of a polymer containing at least acrylonitrile in polymerized form, an inert solvent for said polymer, and from about 3% to about 20% based on the weight of said polymer of a haloalkyl phosphate having the general formula Ra wherein R R and R are haloalkoxy radicals having alkyl radicals selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl and from 1 to 4 substituted halogen atoms selected from the group consisting of bromine and chlorine washing said filaments in an aqueous bath whereby said solvent is substantially removed from said filaments, and thereafter drying said filaments.
• a filament comprising an acrylonitrile polymer se- I lected from the group consisting of homopolymers of acrylonitrile and copolymers containing at least 70% acrylonitrile and up to 30% of an ethylenically unsaturated monomer copolymerized therewith having included therein from about 5% to about 15% by weight of a haloalkyl phosphate having the general formula wherein R R and R are haloalkoxy radicals having alkyl radicals selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl and from 1 to 4 substituted halogen atoms selected from the group consisting of bromine and chlorine.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Toxicology (AREA)
• Artificial Filaments (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (3)

Citations (5)

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  • NL NL255298D patent/NL255298A/xx unknown
  • NL NL129325D patent/NL129325C/xx active
• 1959
  • 1959-08-27 US US836339A patent/US3149089A/en not_active Expired - Lifetime
• 1960
  • 1960-08-18 GB GB28656/60A patent/GB881211A/en not_active Expired
  • 1960-08-26 FR FR836900A patent/FR1268707A/fr not_active Expired
  • 1960-08-26 DE DEP25587A patent/DE1273743B/de active Pending

Patent Citations (5)

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